Insecticidal composition comprising 2, 2, 4,-4, 6, 6-tris (tetramethylene)-1, 3, 5-trithiane and 2, 2, 4, 4, 6, 6 tris (pentamethylene) 1, 3, 5-trithiane



United States Patent INSECTICIDAL COMPOSITION COMPRISING 2,2,4,-

4,6,6 TRIS (TETRAMETHYLENE) 1,3,5 TRITHI- ANE AND 2,2,4,4,6,6TRIS(PENTAMETHYLENE) l,3,5-T RITHIANE V Francis T. Wadsworth, Dickinson,and Paul D. May, Galveston, Tex., assignors to The American Oil Company,

Texas City, Tern, a corporation of Texas N0 Drawing. Filed May 12, 1958,Ser. No. 734,425

6 Claims. (Cl. 167-33) The present invention relates to insecticidalcompositions and methods for destroying insects, particularly thoseinsects which are of the sucking type. It has been found that2,2,4,4,6,6-tris(tetramethylene)- 1,3,5-trithiane and2,2,4,4,6,6-tris(pentamethylene)-l,3,5- trithiane are highly effectivein destroying insects, particularly insects which are of the suckingtype such as mites, aphids and'the like. In destroying such insects, theinsecticides of this invention are applied to the vegetation. Theinsecticides increase the resistance of the treated vegetation to damageby the sucking insects, inasmuch as the insects which infest the treatedvegetation become poi: soned and destroyed by the insecticide. Theinsecticide is typically applied to the leaves or foliage of vegetation,and it may conveniently be applied by spraying the foliage with watercontaining the insecticide in an amount between about 0.001 and 1.0% byweight. The invention thus includes the treatment !of vegetation toincrease the resistance thereof to damage by insects of the suckingvariety and also includes compositions which are useful for such apurpose. The compositions include 2,2,4,4,6,6- tris(tetramethylene)1,3,5 trithiane, .2,2,4,4,6,6 tris-- (pentamethylene) -l,3,5-trithiane,and .mixtures thereof which have been diluted with water to aconcentration between 0.001% and 1.0% by weight, and concentrates whichare useful in forming such dilute compositions. A composition such ascontains between 10 to 50% by weight of the trithiane, between about 1to by weight of an emulsifier, and the remainder a hydrocarbondistillate is exemplary of concentrates which may be diluted with waterto form the composition containing between 0.001% and 1.0% by weight ofthe trithiane which is applied to the vegetation.

The 2,2,4,4,6,6-t1is(tetramethylene)-1,3,5-trithiane has the followingstructural formula:

H24) 7 CH2 CHz-CH: S

C CHa-CH: S S

It may be prepared by slowly adding hydrogen sulfide and gaseoushydrogen chloride to cyclohexanone at about A 2,943,977 Patented July.5, 1960 0 C. and recovering the crystalline melting point of about 101C.

Sucking-type insects are quite harmful to vegetation since they extractjuices from the leaves and frequently stunt or cause destruction of thevegetation. Trees, shrubs, vegetable plants, and the many varieties ofsuch vegetation are seriously damaged by this type of insect. Fruit andvegetable crops are reduced in size because of the damage caused by suchinsects. Typical of this variety of insect are those of the homopteragroup which include aphids, scale insects, cicada, leafhoppers, spittlebugs, those of the hemipter'a group such as squash bugs, stink bugs,milkweed bugs, and others such as mites and the like. I

When the trithiane is applied to the vegetation, it is effective indestroying the sucking variety of insects and therefore increases theresistance of the treated vegetation todamage by the insects. It isbelieved that the insecticide functions as a contact poison, the insectbeing destroyedby coming in contact with the trithiane. The insecticidemay be applied to the vegetation either during the dormant stage of thevegetation or during its stage of active growth. It is generallypreferred to apply this type of insecticide to vegetation during itsstage of active growth. This may be doneby diluting the insecticide withwater until the concentration of the insecticide in' product which has awater is between 0.001% and 1.0% by weightyand then applying this waterdiluted insecticide by spraying or other suitable technique to theleaves of the vegetation, usually in amounts to completely wet theleaves. Greater or lesser concentrations may beused, depending upon theparticular insect which is to be destroyed, variations in sprayingtechniques, weather conditions, etc. Typically H a concentration of from0.01 to 0.1% byweight of the insecticide in water will be satisfactoryfor destroy ing a wide variety of insects of the sucking type.

For purposes of commercial distribution it is desirable to have aconcentrate of the insecticide which may be easily diluted with water toform the aqueous composition which is applied. Typical of suchconcentrates is one containing between about 10% to 50% by weight of thetrithiane, between about 1 to 15% by weight of an emulsifier, and theremainder a hydrocarbon distillate. The trithianes are oil-soluble andan emulsifier is desirable in order to emulsify the trithiane and oil inthe water, forming an oil-in-water emulsion. Any emulsifier whichfunctions in such manner can be used. A typical emulsifier is Tween 80,which is a fatty acid ester of anhydrosoribtol which has been condensedwith ethylene oxide. Span 80, Victawet 12, and many other non-ionicemulsifying agents in addition to the Tween may also be used for thispurpose. Various anionic and cationic emulsifiers may also be employed.The hydrocarbon distillate used in the concentrate is one such as apetroleum distillate. Although wide varieties of petroleum distillatesmay be used, a petroleum oil which is relatively free of aromatics orhas only a low concentration thereof is somewhat preferred. After thisconcentrate is diluted with water it is then applied to the vegetation,particularly to the leaves thereof, by typical spraying means such asmechanical ground sprayers, hand sprayers, etc.

Since the insecticide is a solid at atmospheric temperatures, it may beapplied to the vegetation by dusting techniques. This is commerciallydone by mixing the insecticide with an inert powder and thendistributing the diluted powdered insecticide by mechanical means fromthe ground or from the air.

When the insecticide is applied to the vegetation during its dormantperiod, such as during the winter time, this may conveniently be done byadding the insecticide to a leaveshadlbeenrdestroyegl.

dormant oil and thenspraying the latter onto bark of trees, shrubs orthe like beneath which the insects gather. Any conventional dormant oil,i.e. a hydrocarbon distillate which is low in aromatics, may be used.The ins'ecticide maybe contained inthe oil in amounts between 0.001% and1.0% by weight, as hereinabove discussed.

- 1 Example 1, Leaves werejinf estedwith green peach aphids. The leaves.infested with the aphids were then sprayed until dripping wet, using anaqueous solution containing 0.1% by 'weight; of 2,2,4,4,6,6-t'ris('tetramethylene)--l,3,5-trithiane. Approximately 24 hourslater the leaves were examined under a microscopeand it was found thatan average of 100% of the aphids on the treated leaves hadbeendestroyedL I t Q Example2 V Another set ;of leaves was infested with"two-spotted Imites. The leaves were then-sprayed until dripping wet,

. using an aqueous solutioncontaining 0.0l25 'byweight V of the latter.

1 What is claimed is:

l. A method for increasing the resistance of vegetation. to damage bysucking insects which comprises applying a trithiane selected from thegroup consisting of -.2,2, 4,6,6v.- tris(tetramethylene) 1,-3,5 -.:trithiane; 2,2,4,4,' 6,6j-tris (pentamethylene)-1,3, 5 trithiane, and ixturesthereof'to'the vegetation. V

2. The method of claim 1 wherein thetritlliane' is applied byvsprayingwater containing between 0.001% and 1.10% by weight of the ,tr-ithianeon the leaves of the vegetation. a a v j a 3. lhe method .of claim. 1wherein the trithiane is applied' by spraying a low aromatics contentdistillatecontaining between 0.001% and 1.0% by weight'of the trithianeto the barkrof vegetation during the dormant stage 4. The method ofdestroying 'suclringi inseet's wh'icii comprises contacting such insectswith a 'tiithiane selected of 2,2,4,4,6,6tris(tetramethylene)-l,3,5-trithiane. Ap-

proximately 24 hours, later the treated leaves were examined under amicroscope. It was found that an aver- "age of about 90% oftheytwo-spotted mites had been destroyed by the treatment.

0.1% a by" weight :of 2;2;4,4,6,6 tris(pentamethylene)-1,3,5-trithiane'. Approximately 24 hours later the leaves were examinedundera microscopeand it was found that an average of about 91% of theaph ds-on :the treated Leaves infested with two-spotted mitesweresprayed hadbeendestroyed bythe treatment. j I v The above examples arenot intended as limiting the scope ,of the invention,but are merelyillustrative of the effectiveness of the insecticides when used ontypical varieties of the sucking-type insects. j

from the group-consisting of 2,2',4,4, 6,6-tris( tetrainethyh ene) 1,3,5trithiane, 2,2,4:,4,6 ,6 tris'(pentamethylene)5 l;3,'5-trithiane, andmixtures thereof.

:5.A composition useful for destroying suckingaype insectswhich'lcomprises a trithiane selected fromgroup consisting of2,2,4,4,'6,6-tris(tetramethylene)-l;3 5-5 trithiane,2,2,4,4;6,6-tris(pentarnethylene)1;3,5-trithiane and :mixtures thereofdiluted with water to' a 7 concentration between about 0.001% and 1.0%by weight. 1 V v .6; A concentrate useful in forming insecticidal rom:

3 5" methylcne)=l,3,5-trithiane, and mixtures thereoffibe tween :about'1 to 15% by weight or an-emuls'ifierg and" the ':remainder ahydrocarbon distillate; sa iaceneeaeate being capable of dilution withwater to form an insecti- V cidal composition. containing between=about'0.001%

1.0% by weightof the trithiane.

References Cited in the file of this patent e I UNITED STATES PATENTSJones et a1 Oct. 5, 1954,

OTHER REFERENCES Frear: A Catalogue of Insecticides and Fungicides; v61;7

5. A COMPOSITION USEFUL FOR DESTROYING SUCKING-TYPE INSECTS WHICHCOMPRISES A TRITHIANE SELECTED FROM THE GROUP CONSISTING OF2,2,4,4,6,6-TRIS(TETRAMETHYLENE)-1,3,5TRITHIANE,2,2,4,4,6,6-TRIS(PENTAMETHYLENE)-1,3,5-TRITHIANE, AND MIXTURES THEREOFDILUTED WITH WATER TO A TRITHIANE CONCENTRATION BETWEEN ABOUT 0.001% AND1.0% BY WEIGHT.